title: Discovery and synthetic applications of novel silicon-carbon bond cleavage reactions based on the coordination number change of organosilicon compounds.
abstract: Some synthetically useful transformations of organosilicon compounds have been developed since the mid 1970s, based on the new concept that the silicon-carbon bonds are activated toward electrophilic cleavage via the formation of penta- and hexa-coordinate species. This review mainly consists of the following aspects: (1) a general concept for the activation of the silicon-carbon bond via penta- and hexa-coordinate species, (2) synthetic application of hexa-coordinate organopentafluorosilicates, and (3) development of the H(2)O(2) oxidation of the silicon-carbon bond and its synthetic applications via the intramolecular hydrosilylation, silicon-tethered intramolecular radical cyclization and Diels-Alder reaction, and some silicon-containing organometallic reagents for nucleophilic hydroxymethylation and hydroxyallylation synthons.(Communicated by Hitosi NOZAKI, M.J.A.).
authors.affiliation: Advanced Science Institute, RIKEN, Saitama, Japan. tamao@riken.jp
authors.forename: Kohei
authors.initials: K
authors.lastname: Tamao
mesh_terms: D002244:Carbon / Q000737:chemistry*; D006861:Hydrogen Peroxide / Q000737:chemistry; D017646:Organosilicon Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010084:Oxidation-Reduction; D012825:Silicon / Q000737:chemistry*
chemical_list: D017646:Organosilicon Compounds; D002244:Carbon; D006861:Hydrogen Peroxide; D012825:Silicon